Sulphoaromatic compound of certain higher aliphatic ketones



Patented May 25, 1937 UNITED STATES PATENT OFFICE SULPHOAROMATIC COMPOUND OF CER- TAIN HIGHER, ALIPHATIC KETONES Melvin De Groote, St. Louis, Mo., assignor to Tretolite Company, Webster Groves, Mo., a corporation of Missouri No Drawing. Application June 8, 1936,

. Serial No. 84,180

7 Claims. (01. 260-131) of the kind known as Twitchell reagents. .Suitable fatty acids for the manufacture of Twitchell reagents include erucic acid, oleic acid, etc. Fatty acids containing more than one ethylene linkage,

such as linoleic acid or linolenic acid, may be employed. Similarly, hydroxy-stearic acid or di-f hydroxy-stearic acid may be employed. Ricin-/ oleic acid may be employed. Ricinoleic acid re acts with sulphuric acid at the alcohol hydroxyl in preference to' the ethylene linkage. Hydrogenated ricinoleic acid, in which the hydroxyl is intact, may be employed. Acetylated ricinoleic may be used. The various fatty acids or their more available form, such as the glyceride, of the kind specified, are characterized by the fact that they react with sulphuric acid to form acid sulphates.

It is well known that various fatty acids may be treated in various manners to yield ketones. Reference is made to Chemical Technology and Analysis of Oils, Fats, and Waxes, sixth edition (1921), volume 1, pp. 146 and 153. It is to be noted that certain fatty ketones, such as oleone and erucicone, described by Lewkowitsch, are characterized by the presence of an ethylene linkage in each of the two fatty acid residues which enter into the composition of the compound. Such ketones will react with sulphuric acid to form acid sulphates which decompose at least slowly in presence of dilute acid to reliberate sulphuric acid. Similar ketones,such as hydroxystearone, dihydroxy-stearone, ricinoleone, etc., may be prepared by similar methods. The preparation of the higher ketones is usually conducted in the manner indicated by Lewkowitsch, to-wit, heating the fatty acids with iron filings to. about 350 C. In the subsequent description, I shall referto oleone, because it is the cheapest available higher fatty ketone; but it is to be understood that any of the higher fatty ketones which react with sulphuric acid to form acid sulphates may be employed.

I have found that when one molecular'weight of oleone, or a similar material, is mixed with one or two molecular weights of a suitable aromatic compound of the same kind which is customarily .tible to Twitchell condensation.

employed in the manufacture of Twitchell reagents, and when said mixture is subjected to sulphonation in a manner employed in the manufacture of Twitchell reagents or in the manner employed in the sulphonation of various fatty acids, or fatty compounds, one obtains a new chemical compound. Sucha product is characterized by the fact that one or two sulphoaromatic residues are introduced so as to form addition products or substitution products of the m particular higher fatty ketonewhich is being employed. In the use of oleone, the ethylene linkage disappears with complete saturation by introduction of a hydrogen atom and a sulphoaromatic residue, thus forming an addition prod- 15 not. In the employment of hydroxy-stearone, the sulphoaromatic residue replaces the alcoholic hydroxyl, and thus is' a substitution product. In some instances, and especially where it is desirable to obtain'light-colored products, I have found that the method employed in producing certain sulphoaromatic compounds, such as sulphoaromatic derivatives of hendecenoic acid is desirable. This method involves sulphonation in presence of certain organic acids or their anhydrides and is limited to use with non-hydroxy ketones. Such procedure is described in U. S. Patent 2,030,492, dated April 9, 1936, to De Groote and Keiser.

In the manufacture of Twitchell reagents, the 30 aromatic materials customarily employed are benzene, naphthalene, phenol, cresol, etc. Toluene and xylene are sometimes employed; Beta naphthol is'sometimes employed. Tetralin may be employed.- Anthracene, hydrogenated anthra- 35 cene or phenanthrene have been'found useful in the manufacture of such sulphoaromatic fatty acids. These aromatic substances employed are characterized by the' fact that they produce monosulphonic acids when treated with sulphuric acids of properstrength and under the proper conditions, and are also characterized by the fact that when such sulphonic acids are contacted with higher fatty acid sulphates, such as the acid sulphate derived from oleic acid, that condensation takes place, presumably with the elimination of sulphuric acid. Aromatic compounds of this kind-are commonly referred to as being suscep- A molecule of oleone may be admixed with one molecule-of benzene, or two molecules of benzene,

' or with one or two molecules of phenol,- or with one or two molecules of naphthalene. It is also obvious that two different aromatic materials might be ,employedyfor instance, one molecule of oleone may be mixed with. one molecule of phenol and one molecule of naphthalene. The sulphonation process, of course, is conducted after mixture, but it is also evident that one might convert the aromatic material into a sulphonic acid and convert the selected ketone into a mono-acid sulphate or a di-acid sulphate, prior to admixture with the aromatic material.

It is to be noted that if one has the ketone of an unsaturated hydroxy acid, such as ricinoleone, not only will it be hypothetically possible tointroduce a sulphoaromatic residue at each ethylene linkage, but also at each alcoholiform hydroxyl. However, if such materials are formed at all, apparently they are relatively unstable, or else their formation is prevented by some phenomenon such as steric hindrance. If one had available the ketone derived from an unsaturated hydroxy acid in which the" separation in the hydrocarbon chain between the alcohol hydroxyl and the ethylene linkage happened to be greater than in the case of ricinleone, then possibly three or four sulphoaromatic residues could be so introduced.

It is understood, of course, that more than one sulphonic acid residue may be introduced into the aromatic nucleus. For instance, instead of introducing one sulphonic acid residue into a naphthalene nucleus, one might substitute two or even more.

It is possible that subsequently there may be- .come available higher fatty ketones derived from two different fatty acids; for instance, a ketone derived from one molecule of oleic acid and one molecule of stearic acid. It is apparent that as long as one of the fatty residues entering into the composition of the ketone contains an ethylene linkage or an alcoholiform hydroxyl, such a mixture ketone would be satisfactory for producing the type of material herein contemplated.

Oleone, (C11H33)2C0, prepared by treatment of oleic acid with iron filings at about 350 C., is treated with sulphuric acid monohydrate at a relatively low temperature, approximately 10 to 30 C., until the product is converted into the di-acid sulphate of the composition Similarly, phenol is converted into phenol sulphonic acid in the conventional manner. It is unnecessary to separate either the sulphonated aromatic material or the sulphated ketone from the excess acid employed in sulphonation in one instance, and in sulphation in the other instance. The acid masses are mixed in such proportion that 700 pounds of (C1'1H34'HSO4)2CO is mixed with 350 pounds of phenol sulphonic acid. This calculation is based on the assumption that all the oleone was converted into the hydrogen sulphate and that all the phenol was converted into phenol sulphonic acid. The above mixture is intended to combine two molecules of phenol sulphonic acid with one molecule of After combining the two acid masses, the mixture is stirred cautiously at a temperature of about 30-35 C. and the temperature raised carefully to slightly under 40 C., if need be, until condensation has taken place and a compound of the following composition formed:

(C1'1Ha4OH- CsHa HSOs) 2C0 If condensation or combination does not take place readily enough, it may be desirable to add oleum containing 20%, 25% sulphur trioxide in relatively small amounts, for instance, 5% by weight of the total acid mass. The reaction should go to completion within 10-30 hours, and in some instances is substantially complete within four or five hours or even less.

Completion of reaction can be determined in the following manner: A small amount of the acid mass is diluted with three or four volumes of water and boiled under reflux condenser for approximately 30 minutes. It is then poured into a separatory funnelandthelower layer of dilute acid withdrawn. The upper oily layer is then diluted with a large excess of water and should produce a clear solution which indicates that the entire mass is water soluble, due to the formation of the fore the step of separation and subsequent dilution is necessary.

At the completion of the reaction, the acid mass is diluted with approximately twice its volume of 'cold water and the mixture stirred until homogeneous. The mixture is allowed to separate and the lower layer consisting of dilute acid is withdrawnand discarded, the upper layer representing (CnHn-OH-CaHa-HSOa)2C0. It is then employed in its acid state or is neutralized in any suitable manner. It may be neutralized with such materials as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or the corresponding carbonates or bicarbonates. It may be neutralized with such materials as calcium or magnesium oxides or hydroxides. It may be neutralized with a suitable amine, such as triethanolamine, butylamine, amylamine, benzylamine, cyclohexylamine, aniline, etc. Some of the products so obtained not only are soluble in water, but are also soluble in hydrophobe vehicles such as gasoline or kerosene. Some compounds may be oil soluble and rather insoluble in water. Salts of the heavy metals, such as iron, copper, and the like, can also be obtained if desirable. It is my preference to convert the ma.- terial above described into the sodium salt having. the composition '(C1'lH34'OH-CsH3NaSO3)2C0.

-can thereafter be converted into sulphoaromatic derivatives of the kind herein described.- For practical purposes, then the ketones employed to form the products herein described must be derived from fatty acids of their derivatives capable of forming acid sulphates, and said fatty acids must come within the molecular weight range indicated by the variation from hendecenoic acid,

CuH2uO2, to erucic acid, (722E002.

' The presence of more than one sulphonic acid residue, in one or more of the aromatic nuclei, increases water solubility.

As previously pointed out, an acidic hydrogen atom may be present in the compound as such or it may be neutralized or esterifiedso that it is replaced by a metallic atom, ammonium radical amine residue or radical, or by an organic radical such as an alkyl radical or aryl radical. The expression ionizable hydrogen equivalen is employed to indicate such acidic hydrogen atom or its equivalent of the kind indicated.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A new chemical compound consisting of sulphoaromatic derivatives of ketones obtained by sulphonation and condensation reactions involving aromatic compounds of the kind which are susceptible to Twitchell condensation and allphatic ketones'derived from fatty acids having at least l1 carbon atoms and not more than 22 carbon atoms, said ketones bein'g additionally characterized by being susceptible to sulphation.

2. A new chemical compound consisting of sul-. phoaromatic derivates of ketones of the kind indicated by the type formula.

in which Rrepresents the radica1-R"-T-SO:|-Z

and R represents the radical- "-T'-SO:Z, in which R" represents a residue derived from a fatty acid having at least 1 1 carbon atomsand.

" not more than 22 carbon atoms in the chain and susceptible to sulphation; T and T' represent an aromatic residue derived from an aromatic Patent No. 2,081,795.

Certificate of Correction MELVIN DE GROOTE body susceptible to Twitchell condensation; S0:

is the conventional sulphonic acid residue: and Z is an ionizable hydrogen atom equivalent: both fatty acid residues indicated by R." being identical.

4. A new chemical compound consisting of sulphoaromatic derivatives of ketones of the kind indicated by'the type formula in which R. represents the radicalR'-T-SOa-Z in whichR' represents a residue derived from a fatty acid having at least 11 carbon atoms and not more than 22 carbon atoms in the chain and susceptible to sulphation; T represents an aromatic residue susceptible .to Twitchell condensation; S0: is the conventional sulphonic acid residue; and Z is an ionizable hydrogen atom equivalent; both fatty acid residues indicated by R being identical and both aromatic residues indicated by 'I' being identical,

5. Y A new chemical compound consisting of sulphoaromatic derivatives of ketones of the kind indicated by the type formula in which R represents the radical-IV-T-SOarZ.

in which R. represents a residue derived from a fatty acid having at least .11 carbon atoms andnot more than 22 carbon atoms in the chain and susceptible to sulphation; T represents a monocyclic aromatic residue susceptible to Twitchell condensation; S0: is the conventional sulphonic acid residue; and Z is an ionizable hydrogen atom equivalent.

6. A new chemical compound consisting of sulphoaromatic derivatives of ketones of the kind indicated by the type formula n i in which R. represents the radicalR'-T-SOa-Z. in which R represents a residue derived from a fatty acid having at least 11 carbon atoms and not more than 22 carbon atoms in the chain and susceptible to sulphation; T represents a. phenol residue; 803 is the conventional sulphonfc acid residue; and Z is an ionizable hydrogen atom equivalent.

'7. A new chemical compound indicated by the formula (C11H34'OH'CcI-I3'NaSOa) 2C0.

mvm DE Grtoo'm.

May 25', 1937,

It is hereby certified that errors appear in the printed specification 'of the abovenumbered patent requiring correction as follows: Page 2,'first column, lines 48 and 66, and second column, hne 21, for the formula C H -HSO COV read (0 E HSOQ OO; and that the said Letters Patent" should be read. with these corrections therein that the same may conform to the record of the casein the Patent Ofiice.

Signed and sealedthis 20th day'of July, A. D. 1937.

[SEAL] 

